NL8603048A - SUCCINIMIDE COMPLEXES OF BORATE-TREATED ALKYLATE TECH AND LUBRICATING OIL COMPOSITIONS CONTAINING THESE COMPLEXES. - Google Patents

Description

N.0. 34207 1 "

Field of the invention Succinimide complexes of borate-treated alkyl catechol and lubricating oil compositions containing these complexes.

The invention relates to the product obtained by reacting a borate-treated alkyl catechol with a sucinimide and the use of this product in lubricant compositions.

5 2. Description of the prior art

Due to the crisis, which is associated with decreasing amounts of phosphil fuel and the rapidly rising prices for this fuel, there is a great deal of interest in reducing the amount of fuel consumed by automobile engines and the like.

There is therefore a great need to find lubricants which reduce the total friction in the engine, thus reducing the energy needs for it.

U.S. Patent 2,795,548 describes the use of lubricant compositions containing borate-treated alkyl catechols. The oil compositions are used in the crankcase of an internal combustion engine to reduce oxidation of the oil and corrosion of the metal parts of the engine.

There is a problem with the use of borate-treated alkyl catechols in lubricating oils since they are moisture sensitive and readily hydrolyze. The hydrolysis leads to cloudiness and / or precipitate formation, which must be filtered out before use.

It has now been found that the borate-treated alkyl catechol and can be stabilized against hydrolysis by complexing the borate-treated alkyl catechol with an alkenyl or alkyl mono- or bis-succinimide.

Most importantly, it has now been found that lubricating the crankcase of an internal combustion engine with a lubricating oil containing the reaction product of a borate-treated alkyl catechol and a sucquinimide reduces the fuel consumption of the engine.

Summary of the invention

According to the present invention, lubricating oils are provided which reduce the friction between sliding metal surfaces and which are particularly suitable in the crankcase of internal combustion engines. The reduced friction results from the addition to the lubricating oil of small amounts of a complex prepared by reacting a borate-treated alkyl catechol and an alkyl 860 3 04 8 λ i 2 or alkenyl mono- or bis-succinimide.

Thus, in one aspect, the present invention relates to a lubricating oil composition containing an oil of lubricating viscosity and an effective amount to reduce the friction of a complex prepared by reaction (a) of a borate-treated alkyl catechol and ( b) an oil-soluble alkyl or alkenyl mono- or bis-succinimide.

Other additives may also be present in the lubricating oil to achieve an appropriate balance of properties, such as dispersive power, corrosion, wear inhibition and oxidation, which are critical to the proper operation of an internal combustion engine.

According to still another aspect of the present invention, there is provided a method of reducing the fuel consumption of an internal combustion engine by treating the moving surfaces thereof with the lubricating oil composition described above. More specifically, improvements in the mileage of the fuel of 1 to 2% can be achieved by applying the composition of the present invention. This improvement in the fuel economy can be achieved in both compression ignition engines, that is, diesel engines, and spark ignition engines, that is, gasoline engines.

In addition, it has been found that lubricating oil compositions containing the borate-treated alkyl catechol succinimide complex of the present invention also have antioxidant properties and when used in diesel engines, they have an inhibition of the diesel deposit.

The complex between the borate-treated alkyl catechol and the alkenyl or alkyl succinimide can be prepared in situ. That is, when borated alkyl catechol and a sufficient amount of alkenyl or alkyl succinimide are added to the lubricating oil to stabilize the borated alkyl catechol against hydrolysis, the complex is formed in situ.

In this regard, the present invention relates to a lubricating oil composition comprising an oil of lubricating viscosity and an effective amount to reduce the friction of a borate-treated alkyl catechol and an effective amount of an alkenyl succinimide around the borate-treated alkyl catechol against hydrolysis. to stabilize.

40 When used in this manner, other additives may also be present in the lubricating oil to add a suitable balance of properties such as dispersion, corrosion, wear and oxidation critical to the proper operation of an internal engine combustion.

Therefore, another aspect of the present invention is a lubricating oil composition, which is particularly suitable in the crankcase of an internal combustion engine for the purpose of improving the fuel consumption of this engine, which (a) contains a major amount of an oil of lubricating viscosity and (b) an effective amount of any of the following: 1. an alkenylsuccinimide, 2. a Group II metal salt of a dihydrocarbydithilophosphoric acid, 3. a neutral or overbased alkali metal. - or alkaline earth metal hydrocarbyl sulfonate or mixtures thereof, 4. a neutral or overbased alkali metal or alkaline earth metal alkylated phenolate or mixtures thereof, and 5. a borate treated alkyl catechol as a friction modifier.

In accordance with yet another aspect of the present invention there is provided a method of reducing the fuel consumption of an internal combustion engine by treating its moving surfaces with the lubricating oil composition described above.

DETAILED DESCRIPTION OF THE INVENTION

The borate-treated alkyl catechol and are prepared by converting an alkyl catechol with boric acid to remove the reaction water to the borate. Preferably, sufficient boron is present so that any boron will react with 1.5 to 2.5 hydroxyl groups present in the reaction mixture.

The reaction can be carried out at a temperature in the range of from 60 ° C to 135 ° C, in the absence or presence of any suitable organic solvent such as methanol, benzene, xylenes, toluene, neutral oil and the like.

The alkyl catechols or mixtures thereof which can be used to prepare the borate-treated alkyl catechoes used in the present invention are preferably monoalkyl catechol and of the formula 1 wherein R is alkyl having 10 to 30 carbon atoms and preferably 16 up to 26 carbon atoms. Also, up to 40% by weight, but preferably less than 10% by weight, of the monoalkylcate-8603048 ii 4 cholesterol, may have the group R in a position adjacent to or ortho to one of the hydroxyl groups and have the formula 2, wherein R is as defined above.

Also included in the alkyl catechol and which can be used for the preparation of the borate-treated alkyl catechol and of the present invention are dialkyl catechol and which are generally of the formula 3 wherein R is as defined above. Trialkylca-techols can also be used, although they are not preferred.

Among the alkyl catechol and which may be used are decyl catechol, undecyl catechol, dodecyl catechol, tetradecyl catechol, penta decyl catechol, hexadecyl catechol, octadecyl catechol, eicosyl catechol, hexacosyl catechol, such as. Also, a mixture of alkyl catechol and may be used, such as a mixture of C 14 -C 14 alkyl catechol and or a mixture of C 8 -C 2 alkyl catechol and may be used.

The alkyl catechol and of the formula III can be prepared by reacting an olefin having 10 to 30 carbon atoms, such as a branched olefin or a straight chain alpha olefin containing 10 to 30 carbon atoms, with pyrocatechol in the presence of a sulfonic acid catalyst at a temperature of about 60 ° C to 200 ° C and preferably 125 ° C to 180 ° C in a substantially inert solvent at atmospheric pressure. Examples of inert solvents include benzene, toluene, chlorobenzene and Thinner 250, which is a mixture of aromatics, algae and naphthenes.

The term "branched olefin" means that branching occurs at the double bond. The term "straight chain α-olefin" means that the α-olefin contains little (less than 10%) or no branching at the double bond or elsewhere.

A product, which is predominantly monoalkyl catechol, can be prepared using reagent molar ratios, and preferably a 10% molar excess of branched olefin or α-olefin to catechol is used. When used at molar ratios, the resulting products are generally monoalkylcatechols, but contain some amount of dialkylcatechol. In any case, a molar excess of pyrocatechol (i.e., 2 equivalents of pyrocatechol or any equivalent of olefin) can be used to enhance the monoalkylation when predominantly monoalkylcatechol is desired. Predominantly dialkyl catechol and can be prepared using two 40 equivalents to pyrocatechol of the same or a different

860304S

* ί 5 already.

The use of a branched olefin results in a greater amount of alkyl catechol and of formula 1 than the use of straight chain alpha olefins. The use of such branched olefins generally results in more than 90% alkyl catechol of formula 1 and less than 10% alkyl catechol of formula 2.

The borate-treated alkyl catechols are stabilized against hydrolysis by reacting the catechols with an alkyl or alkenyl mono- or bis-succinimide. In the preferred embodiment, an alkyl or alkenyl monosuccinimide is used.

The oil-soluble alkenyl or alkyl mono- or bis-succinimides used in the present invention are generally known as lubricating oil detergents and are described in U.S. Pat. Nos. 2,992,708, 3,018,291, 3,024,237, 3,100. 673, 3,219,666, 3,172,892, and 3,272,746. The alkenyl succinimides are the reaction product of a polyolefin-substituted succinic anhydride with an amine, preferably polyalkylene polyamine. The polyolefin polymer substituted succinic anhydrides are obtained by reacting a polyolefin polymer or a derivative thereof with maleic anhydride. The succinic anhydride thus obtained is reacted with the amine compound. The preparation of the alkenyl succinimides has been described many times in the art. See, for example, U.S. Patents 3,390,082, 3,219,666 and 3,172,892. The reduction of the alkenyl-substituted succinic anhydride gives the corresponding alkyl derivative. A product containing predominantly mono- or bis-succinimide can be prepared by controlling the molar proportions of the reagents. Thus, for example, if 1 mole of amine is reacted with 1 mole of the alkenyl or alkyl substituted succinic anhydride, a predominantly mono-succinimide product will be prepared. When 2 moles of the succinic anhydride are converted per mole of polyamine, a bis-succinimide will be prepared.

Particularly good results are obtained with the lubricating oil compositions of the present invention when the alkenyl succinimide is a mono-succinimide prepared from a polyisobutylene-substituted succinic anhydride of a polyalkylene polyamine.

The polyisobutene of the polyisobutene-substituted succinic anhydride is obtained by polymerization of isobutene and can vary considerably in its compositions. The average number of 40 carbon atoms can range from 30 or less to 250 or more, with 860 3 04 8

* J

6 a resulting number average molecular weight of about 400 or less to 3,000 or more. Preferably, the average number of carbon atoms per polyisobutylene molecule will range from about 50 to about 100 with the polysiobutenes having a number average molecular weight from about 600 to about 1,500. More preferably, the average number of carbon atoms per polyisobutene molecule ranges from about 60 to about 90 and the number average molecular weight ranges from about 800 to 1,300. The polyisobutene is reacted with maleic anhydride by well known methods to form the polyisobutene substituted succinic anhydride. See, for example, U.S. Patent Nos. 4,388,471 and 4,450,281.

In the preparation of the alkenyl succinimide, the substituted succinic anhydride is reacted with a polyalkylene polyamine to form the corresponding succinimide. Each alkylene group 15 of the polyalkylene polyamine usually has up to about 8 carbon atoms. The number of alkylene groups can vary up to about 8. The alkylene group is, for example, ethylene, propylene, butylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, etc. Generally, the number of amino groups, but not necessarily, is one greater than the number of alkylene groups present in the amine that is, when a polyalkylene polyamine contains 3 alkylene groups, it will usually contain 4 amino groups. The number of amino groups can vary up to about 9. Preferably, the alkylene group contains about 2 to about 4 carbon atoms and all amine groups are primary or secondary. In this case, the number of amine groups exceeds the number of alkylene groups by 1. Preferably, the polyalkylene polyamine contains 1 to 5 amine groups. Specific examples of the polyalkylene polyamines include ethylene diamine, diethylene triamine, triethylene tetramine, propylene diamine, tri propylene tetramine, tetraethylene pentamine, trimethylene diamine, pentaethylene hexamine, di (trimethylene) triamine, tri (hexamethylene) tetramine.

Other amines useful for the preparation of the alkenylsuccinimide which are useful in the invention include the cyclic amines such as piperazine, morpholine, and dipiperazines.

Preferably, the alkenyl succinimides used in the compositions of the present invention have the formula 4, wherein: a. Represents an alkenyl group, preferably a substantially saturated hydrocarbon prepared by polymerizing aliphatic monoalkenes. Preferably, it is prepared from isobutene and has an average number of carbon atoms and a number average molecular weight of * 860 3 04 8 * * 7 as described above; b. the "alkylene" group represents a substantially hydrocarbon group containing up to about 8 carbon atoms and preferably about 2 to 4 carbon atoms as described above, 5 c. A represents a hydrocarbyl group, an amine-substituted hydrocarbyl group or hydrogen. The hydrocarbyl group and the amine-substituted hydrocarbyl groups are generally the alkyl and amine-substituted alkyl analogs of the above-described alkylene groups. Preferably A represents hydrogen, 10 d. n represents an integer from about 1 to 10 and preferably from about 3 to 5.

The alkenyl succinimide is present in the lubricating oil compositions of the present invention in an amount effective to stabilize the borate-treated alkyl catechol and against hydrolysis and to act as a dispersant and the deposit of impurities formed in the oil during prevent the operation of the engine.

The correct structure of the complex of the present invention is not known. Certainly, however, while the present invention is not limited to some theory, it is believed to be compounds in which boron has been complexed by whether it is salt of one or more nitrogen atoms of the basic nitrogen present in the succinimide. Therefore, it is preferred that the alkenyl succinimide contains at least 2 and preferably 3 to 5 basic nitrogen atoms.

The complex can be formed by reacting the borate-treated alkyl catechol and the succinimide unmixed at a temperature above the melting point of the reagent mixture and below the decomposition temperature or in a diluent in which the reagents are soluble. For example, the reagents can be combined in the appropriate ratio in the absence of a solvent to form a homogeneous product which can be added to the oil, or the reagents can be combined in the appropriate ratio in a solvent such as toluene or chloroform. solvent are stripped and the complex thus formed can be added to the oil. Also, the complex can be prepared in a lubricating oil as a concentrate containing about 20 to 90% by weight of the complex, which concentrate can be added in appropriate amounts to the lubricating oil in which it is to be used or the complex can be directly the lubricating oil in which it is to be used.

8603048 4% 8

Preferably, the diluent is inert to the reagents and molded products and is used in an amount sufficient to ensure solubility of the reagents and to allow the mixture to be stirred efficiently.

Temperatures for the preparation of the complex can be in the range of from about 25 ° C to 200 ° C, and preferably from 25 ° C to 100 ° C, depending on whether the complex is prepared unmixed or in a diluent, ie lower temperatures can be used when a solvent is used.

An effective amount of succinimide is added to stabilize the borate-treated alkyl catechol and against hydrolysis. Generally, weight percent ratios of succinimide to borate-treated alkyl catechol used to form the complex are in the range of 3: 1 to 16: 1, and preferably 3: 1 to 10: 1, and most preferably 3 : 1 to 6: 1. The latter ratio is preferred when the complex is made unmixed and / or stored or in the absence of solvent or lubricating oil and under atmospheric conditions.

As used herein, the term "stabilized against hydrolysis" means that the borate-treated alkyl catechol succinimide complex does not form a precipitate due to the hydrolysis of the borate-treated catechol for a period of at least 3 months when stored at room temperature (about 15-25 ° C) and moisture from the environment.

The amount of the complex required to be effective in reducing friction in lubricating oil compositions can range from 0.5 to 20% by weight. In the preferred embodiment, however, it is desirable to add sufficient complex such that the amount of borate-treated catechol is added in a range from 0.1 to about 4% by weight of the total lubricating oil composition and is preferably present in the range from 0 , 2 to 2% by weight and most preferably 0.5 to 1¾. The succinimide is present in the complex of the invention in an amount effective to stabilize the borate-treated alkyl catechol against hydrolysis and allow the borate-treated alkyl catechol to function as active friction reducing agents.

Also, the succinimide in the complex acts as a dispersant and prevents the build-up of impurities that are formed in the oil during engine operation.

In general, the complexes of the present invention 860 3 04 8 9 can also be used in combination with other additive systems in conventional amounts for a known purpose.

For example, for use in modern crankcase lubricants, the above-described base composition will be formulated with additional additives to provide the necessary stability, detergent, dispersant, anti-wear and anti-corrosion properties.

Therefore, as another embodiment of the present invention, the lubricating oils to which the complexes prepared by reaction of the borate-treated alkyl catechol and succinimides may be an alkali or alkaline earth metal hydrocarbyl sulfonate, an alkali metal or alkaline earth metal phenolate, and a Group II metal salt of dihydrocarbyldithiophosphoric acid.

Also, since the succinimides act as excellent dispersants, additional succinimide can be added to the lubricating oil compositions above the amounts added in the form of the complex with the borate-treated alkyl catechols. The amount of succinimides can vary up to about 20% by weight of the total lubricating oil compositions.

The alkali metal or alkaline earth metal hydrocarbyl sulfonates may be petroleum sulfonates, synthetic alkylated aromatic sulfonates or aliphatic sulfonates, such as those derived from polyisobutylene. One of the more important functions of the sulfonates is to act as a detergent and dispersant. These sulfonates are well known in the art. The hydrocarbyl group must have a sufficient number of carbon atoms to make the sulfonate molecule soluble in oil. Preferably, the hydrocarbyl moiety has at least 20 carbon atoms and can be aromatic or aliphatic, but is usually alkyl aromatic. Most preferred for use are calcium, magnesium or barium sulfonates, which are aromatic in nature.

Certain sulfonates are usually prepared by sulfonating a petroleum fraction with aromatic groups, usually mono- or dialkylbenzene groups, and then forming the metal salt of the sulfonic acid product. Other feeds used to prepare these sulfonates include synthetic alkylated benzenes and aliphatic hydrocarbons prepared by polymerizing a mono- or diolefin, for example, a polyisobutenyl group prepared by polymerizing isobutylene. The metal salts are formed directly or by metathesis using well known methods. The 40 sulfonates can be neutral or overbased with base numbers up to 8603048

B

10 about 400 or more. Carbon dioxide and calcium hydroxide or oxide are the most commonly used product to produce the basic or overbased sulfonates. Mixtures of neutral and overbased sulfonates can be used. The sulfonates are usually used to provide 0.3 to 10% by weight of the total composition. Preferably, the neutral sulfonates are present from 0.4 to 5% by weight of the total composition and the overbased sulfonates are present in 0.3 to 3% by weight of the total composition.

The phenolates for use in the present invention are those conventional products which are the alkali metal or alkaline earth metal salts of alkylated phenols. One of the functions of the phenolates is to function as a detergent and dispersant. Among other things, it prevents the deposition of impurities, which are formed at high temperature during engine operation. The phenols can be mono or polyalkylated.

The alkyl portion of the alkyl phenolate is present to impart oil solubility to the phenolate. The alkyl portion can be obtained from naturally occurring or synthetic sources. Naturally occurring sources include petroleum hydrocarbons, such as white oil and wax. When derived from petroleum, the hydrocarbon moiety is a mixture of different hydrocarbyl groups, the specific composition of which depends on the particular oil stock used as the raw material. Suitable synthetic sources include various commercially available olefins and alkane derivatives which, when reacted with the phenol, yield an alkyl phenol. Suitable groups obtained include butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, eicosyl, triacontyl and the like. Other suitable synthetic sources of the alkyl group include olefin polymers such as polypropylene, polybutene, polyisobutylene and the like.

The alkyl group can be straight or branched, saturated or unsaturated (if unsaturated, preferably containing no more than 2 carbon atoms and generally no more than 1 site of olefinic unsaturation). The alkyl groups will generally contain from 4 to 30 carbon atoms. Generally, when the phenol is monoalkyl substituted, the alkyl group should contain at least 8 carbon atoms.

The phenolate can be sulfurized if desired. It can be neutral or overbased and, if overbased, will have a base number of up to 200 to 300 or more. Mixtures of neutral and overbased phenolates can be used.

The phenolates are usually present in the oil to provide 0.2 to 8603048% 11 27% by weight of the total composition. Preferably, the neutral phenolates are present in 0.2 to 9% by weight of the total composition and the overbased phenolates are present in 0.2 to 13% by weight of the total composition. Most preferably, the overbased phenolates are present in 0.2 to 5% by weight of the total composition. Preferred metals are calcium, magnesium, strontium or barium.

The sulfurized alkaline earth metal alkyl phenolates are preferred. These salts are obtained by a number of different methods, such as treatment of the neutralization product of an alkaline earth metal base and an alkyl phenol with sulfur. Suitably, the sulfur is added in elemental form to the neutralization product and reacted at elevated temperatures to produce the sulfurized alkaline earth metal alkyl phenolate.

When more alkaline earth metal base was added during neutralization than was necessary to neutralize the phenol, a basic sulfurized alkaline earth metal alkyl phenolate is obtained. See, for example, the method of U.S. Pat. No. 2,680,096.

Additional basicity can be obtained by adding carbon dioxide to the basic sulfurized alkaline earth metal alkyl phenolate. The excess alkaline earth metal base can be added following the sulfurization step, but is conveniently added at the same time as the alkaline earth metal base is added to neutralize the phenol.

Carbon monoxide and calcium hydroxide or oxide are the most commonly used products to produce the basic or "overbased" phenolates. A method in which basic sulfurized alkaline earth metal alkyl phenolates are produced by the addition of carbon dioxide is shown in U.S. Patent 3,178,368.

The Group II metal salts of dihydrocarbyldithiophosphoric acids 30 exhibit wear, antioxidation and thermal stability properties. Group II metal salts of phosphorothithioic acids have been previously described.

See, for example, U.S. Patent 3,390,080, columns 6 and 7, which generally describe these compounds and their preparation. Suitably, the Group II metal salts of the dihydro-drocarbyldithiophosphoric acids useful in the lubricating oil composition of the present invention contain from about 4 to about 12 carbon atoms in each of the hydrocarbyl groups and may be the same or different and aromatic, alkyl or cycloalkyl. Preferred hydrocarbyl groups are alkyl groups containing from 4 to 8 carbon atoms represented by butyl, isobu 860 3 04 8

M W

12 tyl, sec.butyl, hexyl, isohexyl, octyl, 2-ethyl hexyl and the like. The metals suitable for the formation of these salts include barium, calcium, strontium, zinc and cadmium, of which zinc is preferred.

Preferably, the Group II metal salt of a dihydrocarbyldithiophosphoric acid has the formula 5, wherein e. R2 and R3 each independently represent hydrocarbyl groups as described above and f. a cation of a Group II metal as described above.

The dithiophosphoric acid salt is present in the lubricating oil composition of the present invention in an amount effective to inhibit wear and oxidation of the lubricating oil. The amount ranges from about 0.1 to about 4 wt% of the total composition, preferably the salt is present in an amount ranging from about 0.2 to about 2.5 wt% of the total lubricating oil composition. The final lubricating oil composition will usually contain 0.025 to 0.25 wt% phosphorus and preferably 0.05 to 0.15 wt%.

The final lubricating oil can be single or multi-grade. Multiple grade lubricating oils are prepared by adding viscosity index extenders (VI). Usual viscosity index improver and are polyalkyl methacrylates, ethylene-propylene copolymers, styrene-diene copolymers and the like.

So-called rigged VI improvers with both viscosity index and dispersion properties are also suitable for use in the formulations of the present invention.

The lubricating oil used in the compositions of the present invention may be a lubricating viscosity mineral oil or synthetic oils and are preferably suitable for use in the crankcase of an internal combustion engine. Crankcase lubricating oils usually have a viscosity of about 1300 cSt at -17.8 ° C to 22.7 cSt at 99 ° C. The lubricating oils can come from synthetic or natural sources. Mineral oil for use as the base oil in the present invention includes paraffinic, naphthenic and other oils commonly used in lubricant compositions. Synthetic oils include both synthetic hydrocarbon oils and synthetic esters. Suitable synthetic hydrocarbon oils include liquid polymers of ct olefins having the appropriate viscosity. Particularly suitable are the hydrogenated 8603048% c13 liquid oligomers of C6-12 α-olefins, such as 1-decene trimer.

Also, alkylbenzenes of suitable viscosity, such as didodecylbenzene, can be used. Suitable synthetic esters include esters of both monocarboxylic and polycarboxylic acids, as well as monohydroxyal-5 guns and polyols. Common examples are didodecyl adipate, pentaerythritol tetracaproate, di-2-ethylhexyl adipate, diauryl sebacate and the like. Complex esters prepared from mixtures of mono- and dicarboxylic acid and mono- and dihydroxyalkanols can also be used.

Mixtures of hydrocarbon oils with synthetic oils are also suitable. For example, mixtures of 10 to 25 wt% hydrogenated 1-decene trimer with 75 to 90 wt% 150 SUS (37.8 ° C) mineral oil provide an excellent lubricating oil base.

Additive concentrates are also included within the scope of the present invention. They usually comprise about 90 to 15 wt% of a lubricating viscosity oil and about 20 to 90 wt% of the additive complex of the present invention. Usually, the concentrates contain enough diluent to make them easy to handle during transportation and storage. Suitable diluents for the concentrates include any inert diluent, preferably an oil of lubricating viscosity, so that the concentrate can be easily mixed with lubricating oils to prepare lubricating oil compositions. Suitable lubricating oils, which can be used as diluents, usually have viscosities ranging from about 35 to about 500 Saybolt 25 Universal Seconds (SUS) at 37.8 ° C, although an oil of lubricating viscosity can be used.

Other additives which may be present in the formulation include rust inhibitors, foam inhibitors, corrosion inhibitors, metal deactivators, pour point lowering agents, antioxidants and a variety of other well known additives.

The following examples are offered to specifically illustrate the invention. These examples and explanations should not be used in any way to limit the scope of the invention.

EXAMPLES

Example I

Preparation of C 1-8 alkyl Catechol

To a 3 liter flask equipped with stirrer, Dean-Stark trap, 40 cooler and nitrogen inlet and outlet, 759 g of a 860 3 04 8 14

C 14 -C 18 α-olefin (2% C14, 30¾ C15, 30¾ C ^ g, 28¾ C ^ 7 and 10¾ C ^ g), 330 g pyrocatechol, 165 g of a sulfonic acid cation exchange resin (polystyrene cross-linked with divinyl benzene) catalyst (Amberlyst 15 supplied by Rohm and Haas) and added 240 ml of toluene 5. The reaction mixture was heated at 150 ° C to 160 ° C for about 7 hours with stirring under a nitrogen atmosphere. The reaction mixture was stripped by stripping under a reduced pressure (0.05 kPa). The product was filtered hot over supercell (SCC) to give 908.5 g of C 1 -C 18 alkyl substituted pyrocatechol.

The product had a hydroxyl number of 259. Similarly, by substituting an equivalent amount of each of an ot-olefin, a C 14 α-olefin and a C 4 -g α-olefin in the above method, the corresponding alkyl catechol and prepared. Example II

Preparation of C 1 -C 2 alkyl alkyl catechol

759 g of a mixture of C15 to C25 olefin (less than C14 - 2.7%, C14 - 0.3) were added to the 3 liter flask equipped with stirrer, Dean-Stark trap, cooler and nitrogen inlet and outlet. %, C16 - 1.3%, C18 - 8.0%, C20 - 44.4%, C22 - 29.3%, 20 C24 - 11.2%, C26 - 2.2%, C28 - 0.4 %, C30 - 0.2% (containing at least 40% branching (available from Ethyl Corp.), 330 g of pyrocatechol, 165 g of a sulfonic acid exchange resin (polystyrene cross-linked with divinyl benzene) catalyst (Amberlystl available from Rohm and Haas, Philadelphia, Pennsylvania) and 240 ml of toluene was added The reaction mixture was heated at 150 ° C to 160 ° C with stirring under a nitrogen atmosphere for about 7 hours The reaction mixture was heated to 160 ° C under reduced Stripped Pressure (0.05 kPa) The product was filtered hot over diatomaceous earth to give 971 g of a liquid C 1 to C 2 g alkyl substituted pyrocatechol.

Example III

Preparation of a borate-treated C 1 -C 1 -alkyl catechol To 906 g of C 1 -C 1 -g α-alkyl catechol was added 124 g of boric acid and 900 ml of toluene. The mixture was heated at 105 to 118 ° C under a nitrogen atmosphere under azeotropic conditions for about 6 hours. 93 ml of water were collected through a Dean-Stark trap. The reaction product was filtered and stripped on a rotary evaporator under reduced pressure at 155 ° C to give 930 g of the title product.

860 3 04 8 15

Example IV

An oil mixture was prepared as indicated in Table A using CitCon 100 N oil containing 1% by weight of the borate-treated alkyl catechol prepared according to Example III.

5 TABLE A

Formulation Time-days Observation base oil 1-3 clear and pure base oil + 1 wt% formed with borate 1 cloudy and 10 treated alkyl catechol from precipitate example III

Example V

A part by weight of the borate-treated alkyl catechol prepared according to Example III and 3 parts by weight of a 48% by weight polyisobutyl succinimide (prepared by conversion of polyisobutenyl succinic anhydride, in which the number average molecular weight of the polyisobutenyl is about 950 and tetraethylene pentamine in a molar ratio of amine to anhydride of 0.87) solution in oil (CitCon 100 N) 20 were heated together at 100 ° C with mixing on a hot plate for 0.5 hours.

20 ml of the reaction mixture was placed in a 100 ml beaker and stored. A 100 ml beaker containing 20 ml of only the borate-treated alkyl catechol, which had been heated to 150 ° C and containing no suc-cinimide, was also saved for comparison.

The borate-treated alkyl catechol hydrolysed to form a sheet on its surface as it cooled (about 1/4 h).

The borate-treated alkyl catechol succinimide complexed product remained clear and pure after one week of storage. The sample remained pure even after three weeks.

Example VI

Tests were conducted which demonstrated the improvements in fuel economy obtained by adding lubricating oil compositions of the present invention to the automotive engine crankcase.

In this test, a 350 CID Oldsmobile engine was fitted on a dynamometer. An engine lubrication system was devised to provide suitable lubrication to the engine and also provide the ability to change the oil without stopping the engine. In principle, a dry collection system was used with an external pump, which provided lubrication 86 0 5 04 8 16 4 to the engine. This pump was connected by valves to four external collection trays. The placement of the valves determined the oil used.

This run was carried out with base oil and then with the same oil containing 1% by weight of the borate-treated C 1 -C 2 g alkyl catechol prepared according to Example III. The percentage improvements in fuel economy using the compositions of the invention over the base oil are shown in Table B.

10

TABLE B

Fuel economy relative to sample baseline concentrations

Concentration, wt%% improvement 15 1 1.5

The above comparisons were made with fully formulated Exxon 150N oil containing 3.5% of a polyisobutenyl succinimide of tetraethylene pentamine, 30 mmol / kg overbased magnesium hydrocarbyl sulfonphonate, 20 mmol / kg overbased calcium hydrocarbyl sulfonate phenolate, 8.5 mmol / kg zinc 0 , 0-di (2-ethylhexyl) dithiophosphate, 8 mmol / kg of a mixed zinc dialkyl dithiophosphate of sec.butanol, methyl isobutyl carbinol, 0.5% sulfurized calcium polypropylene phenolate, 1.5% of a sulfurized molybdenoic acid succinimide complex and an adequate amount 25 of an amine substituted ethylene / propylene copolymer to provide a 10W30 oil in this formulation and contains an improver.

Also formulated crankcase oils, each containing 0.5 to 2 wt% of borate-treated C13-C24 monoalkyl catechol, borate-treated C14 "C10 dialkyl catechol, and the like instead of the borate-treated alkyl catechol of Example III in the above contain formulations effective in reducing fuel consumption in an internal combustion engine.

860 3 04 8

Claims (20)

A composition containing a complex prepared by reacting a borate-treated alkyl catechol and an oil-soluble alkyl or alkenyl succinimide. The composition according to claim 1, characterized in that the alkyl group of the borate-treated alkyl catechol contains 10 to 30 carbon atoms and the succinimide is a polyisobutenyl succinimide of a polyalkylene polyamine. 3. A composition according to claim 2, characterized in that the succinimide is a polyisobutenyl succinimide of triethylene tetramine or a polyisobutenyl succinimide of tetraethylene pentamine. Composition according to claims 1 to 3, characterized in that the alkyl group of the borate-treated alkyl catechol is a mixture of alkyl groups containing 14 to 26 carbon atoms. Composition according to claim 4, characterized in that the alkyl groups of the borate-treated alkyl catechol is a mixture of alkyl groups containing 14 to 18 carbon atoms. 6. Lubricating oil composition, characterized in that the composition contains a predominant amount of a lubricating viscosity oil and contains an effective amount to reduce the friction of a complex prepared by reacting a borate-treated alkyl catechol and an oil soluble alkyl or alkenyl succinimide. Lubricating oil composition according to claim 6, characterized in that the alkyl group of the borate-treated alkyl catechol is a mixture of alkyl groups with 14 to 26 carbon atoms and the succinimide is a polyisobutenyl succinimide of a polyalkylene polyamine. Lubricating oil composition according to claim 6, characterized in that the alkyl group of the borate-treated alkyl catechol is a mixture of alkyl groups having 14 to 18 carbon atoms. Lubricating oil composition according to claims 6 to 8, characterized in that the succinimide is a polyisobutenyl succinimide of triethylene tetramine or a polyisobutenyl succinimide of tetraethylene pentamine. Method for reducing the fuel consumption of an internal combustion engine, characterized in that the moving surfaces thereof are treated with a composition according to claims 6 to 9. 11. Lubricating oil composition, characterized in that the composition 40 contains a predominant amount of an oil of lubricating viscosity and 860 3 04 8 0.1 to 4% by weight of a borate-treated alkyl catechol and an effective amount of an alkenyl succinimide to borate-treated alkyl catechol to stabilize against hydrolysis. Lubricating oil composition according to claim 11, characterized in that the alkyl group of the borate-treated alkyl catechol contains 10 to 30 carbon atoms and the alkyl succinimide is a polyisobutenyl succinimide of a polyalkylene polyamine. Lubricating oil composition according to claim 12, characterized in that the alkyl succinimide is a polyisobutenyl succinimide of triethylene tetramine or a polyisobutenyl succinimide of tetraethylenepentamine. Lubricating oil composition according to claim 12, characterized in that the alkyl group of the borate-treated alkyl catechol is a mixture of alkyl groups containing 14 to 18 carbon atoms. Lubricating oil composition according to claim 12, characterized in that the alkyl groups of the borate-treated alkyl catechol are a mixture of alkyl groups containing 14 to 26 carbon atoms. 16. Method for reducing the fuel consumption of an internal combustion engine, characterized in that the moving surfaces thereof are treated with a composition according to claim 1. Lubricating oil composition comprising (a) a major amount of an oil of lubricating viscosity and (b) an effective amount of any of the following: 1. an alkenyl succinimide, 2. a borate-treated alkyl catechol, 3. a salt of a Group II metal of a dihydro-carbyldi thiophosphoric acid, 4. a neutral or overbased alkali metal or alkaline earth metal hydrocarbyl sulfonate or mixtures thereof, 5. a neutral or overbased alkali metal or alkaline earth metal alkylated phenolate or mixtures thereof. Lubricating oil composition according to claim 17, characterized in that (1) the alkenyl succinimide is a polyisobutenyl succinimide of a polyalkylene polyamine, (2) the borate-treated alkyl catechol is a borate-treated C 1 -C 20 g alkyl catechol, 860 3 04 8 (3) the metal salt of the dthydrocarbyldithlophosphoric acid is zinc di-alkylthiophosphate, in which the alkyl group contains 4 to 12 carbon atoms, (4) the metal of the neutral or overbased alkali metal or alkaline earth metal sulfonate calcium, magnesium or barium or mixtures thereof (5) the metal of the neutral or overbased alkali metal or alkaline earth metal phenolate is calcium, magnesium or barium. Lube oil formulation according to claim 17, characterized in. 10 that (1) the alkenylsuccinimide is polyisobutenylsuccinimide of triethylene tetramine or polyisobutenylsuccinimide of tetraethylenepentamine, (2) the borate-treated alkyl catechol is a borate-treated C 1 -C 3 alkyl catechol salt, (3) the dihydrocarbyldithiophosphoric acid is zinc 0,0-di (2-ethylhexyl) dithiophosphate, zinc 0,0-di (isobutyl / mixed primary hexyl) dithiophosphate or zinc 0,0-di (sec.butyl / mixed secondary hexyl] dithiophosphate, 20 (4) the metal salt of the sulfonate is an overbased magnesium or calcium hydrocarbyl sulfonate, (5) the metal salt of the phenolate is an overbased sulfurized calcium or magnesium monoalkylated phenolate. 20. Method for reducing the fuel consumption of an internal combustion engine, characterized in that the moving surfaces thereof are treated with the composition according to claim 17. +++++++++++++ 8603048